JP5451131B2 - Method for producing toner for electrophotography - Google Patents
Method for producing toner for electrophotography Download PDFInfo
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- JP5451131B2 JP5451131B2 JP2009070638A JP2009070638A JP5451131B2 JP 5451131 B2 JP5451131 B2 JP 5451131B2 JP 2009070638 A JP2009070638 A JP 2009070638A JP 2009070638 A JP2009070638 A JP 2009070638A JP 5451131 B2 JP5451131 B2 JP 5451131B2
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- 238000002156 mixing Methods 0.000 claims description 63
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- 239000011347 resin Substances 0.000 claims description 30
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- 239000011230 binding agent Substances 0.000 claims description 18
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- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- CVRPSWGFUCJAFC-UHFFFAOYSA-N 4-[(2,5-dichlorophenyl)diazenyl]-N-(2,5-dimethoxyphenyl)-3-hydroxynaphthalene-2-carboxamide Chemical compound ClC1=C(C=C(C=C1)Cl)N=NC1=C(C(=CC2=CC=CC=C12)C(=O)NC1=C(C=CC(=C1)OC)OC)O CVRPSWGFUCJAFC-UHFFFAOYSA-N 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- 125000002947 alkylene group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- Developing Agents For Electrophotography (AREA)
Description
本発明は、電子写真用トナーの製造方法及び電子写真用トナーに関する。 The present invention relates to a method for producing an electrophotographic toner and an electrophotographic toner.
電子写真用トナーの分野においては、電子写真システムの発展に伴い、高画質化及び高
速化に対応したトナーの開発が要求されている。高画質化の観点からは、トナーを小粒径
化する必要がある。
小粒径のトナーには、通常、荷電制御や流動性向上等を目的として外添剤が使用される。例えば、樹脂及び着色剤からなる着色粒子に無機粒子を添加してなるトナーにおいて、体積中位粒径５０〜１０００ｎｍの有機粒子を着色粒子表面に固定化する際に、結着樹脂のガラス転移温度（Ｔｇ）の前後２０℃の温度範囲で、かつ攪拌翼の先端周速４０ｍ／ｓｅｃ以下で粉体を混合する方法（特許文献１参照）や、結着樹脂及び離型剤を含有する母粒子に、Ｔｇ付近の温度でシリカ等の外添剤を混合する方法（特許文献２参照）等が知られている。
In the field of electrophotographic toner, with development of an electrophotographic system, development of a toner corresponding to high image quality and high speed is required. From the viewpoint of high image quality, it is necessary to reduce the particle size of the toner.
In general, an external additive is used for the toner having a small particle diameter for the purpose of charge control and improvement of fluidity. For example, in a toner obtained by adding inorganic particles to colored particles composed of a resin and a colorant, when organic particles having a volume-median particle size of 50 to 1000 nm are immobilized on the surface of the colored particles, the glass transition temperature of the binder resin A method of mixing powder at a temperature range of 20 ° C. before and after (Tg) and at a tip peripheral speed of 40 m / sec or less (see Patent Document 1), or a mother particle containing a binder resin and a release agent In addition, a method of mixing an external additive such as silica at a temperature near Tg is known (see Patent Document 2).
現在、電子写真用トナーに要求される性能はさらに厳しいものとなっており、感光体から紙へのトナーの転写効率は、廃トナー量の低減及び廃トナーの回収容器の小型化による装置の小型化等の目的のため、従来の８０％では足りず、９０％を達成できるものが望まれている。トナーの転写効率の向上のためには、トナーの流動性の向上と付着力の低減が重要である。トナーの付着力の低減にはシリカの多量添加が考えられるものの、シリカの凝集や脱離の問題が発生するのを避けるため、従来は結着樹脂１００重量部に対してシリカを１〜３重量部に抑えざるを得ず、さらなる付着力の低減は困難であった。
そこで、本発明は、転写効率に優れた電子写真用トナーを工業的に生産性良く製造する方法、及び該製造方法により、転写効率に優れた電子写真用トナーを提供することを課題とする。
Currently, the performance required for electrophotographic toners is even more severe, and the transfer efficiency of the toner from the photoconductor to the paper is reduced by reducing the amount of waste toner and downsizing the waste toner collection container. For the purpose of making it easier, the conventional 80% is not sufficient, and what can achieve 90% is desired. In order to improve toner transfer efficiency, it is important to improve toner fluidity and reduce adhesion. Although a large amount of silica can be added to reduce the adhesion of the toner, conventionally, 1 to 3 weights of silica is used per 100 parts by weight of the binder resin in order to avoid problems of silica aggregation and desorption. It was difficult to further reduce the adhesion force.
SUMMARY OF THE INVENTION An object of the present invention is to provide a method for industrially producing an electrophotographic toner excellent in transfer efficiency with good productivity, and to provide an electrophotographic toner excellent in transfer efficiency by the production method.
すなわち、本発明は、下記［１］及び［２］を提供する。
［１］結着樹脂及び着色剤を含有する母体着色粒子１００重量部と、体積中位粒径３０〜１００ｎｍの大粒径シリカ４．０〜７．０重量部とを含有する粉体を、
（ａ）混合羽根を有する混合装置を用いて、混合羽根の先端周速を４０〜８０ｍ／ｓｅｃの範囲、粉体の単位重量当たりに投下する動力エネルギー量を０．０１〜０．０５ｋｗｈ／ｋｇの範囲として混合することにより、（ｂ）粉体の温度を母体着色粒子のガラス転移温度（Ｔｇ）より高い温度に到達させる工程、
を有する電子写真用トナーの製造方法。
［２］上記［１］に記載の製造方法により得られる電子写真用トナー。
That is, the present invention provides the following [1] and [2].
[1] A powder containing 100 parts by weight of matrix colored particles containing a binder resin and a colorant and 4.0 to 7.0 parts by weight of a large particle size silica having a volume median particle size of 30 to 100 nm,
(A) Using a mixing device having a mixing blade, the tip peripheral speed of the mixing blade is in the range of 40 to 80 m / sec, and the amount of power energy dropped per unit weight of the powder is 0.01 to 0.05 kwh / kg. (B) a step of causing the temperature of the powder to reach a temperature higher than the glass transition temperature (Tg) of the base colored particles by mixing as a range of
A method for producing an electrophotographic toner comprising:
[2] A toner for electrophotography obtained by the production method according to [1] above.
本発明によれば、転写効率の優れた電子写真用トナーを工業的に生産性良く製造する方法を提供することができる。該製造方法により得られる電子写真用トナーは、大粒径シリカを母体着色粒子１００重量部に対して４重量部以上用いるにも関らず、大粒径シリカの凝集や脱離が少なく、かつ母体着色粒子表面上への大粒径シリカの均一分散が十分であるため、トナーの付着力が小さく、転写効率に優れ、高い画像濃度が得られる。 ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing the electrophotographic toner excellent in transfer efficiency industrially with sufficient productivity can be provided. The toner for electrophotography obtained by the production method has less aggregation and detachment of the large particle size silica, although the large particle size silica is used in an amount of 4 parts by weight or more with respect to 100 parts by weight of the base colored particles. Since the uniform dispersion of the large particle size silica on the surface of the base colored particles is sufficient, the toner adhesion is small, the transfer efficiency is excellent, and a high image density is obtained.
本発明は、結着樹脂及び着色剤を含有する母体着色粒子１００重量部と、体積中位粒径３０〜１００ｎｍの大粒径シリカ４．０〜７．０重量部とを含有する粉体を、
（ａ）混合羽根を有する混合装置を用いて、混合羽根の先端周速を４０〜８０ｍ／ｓｅｃの範囲、粉体の単位重量当たりに投下する動力エネルギー量を０．０１〜０．０５ｋｗｈ／ｋｇの範囲として混合することにより［以下、条件（ａ）という］、（ｂ）粉体の温度を母体着色粒子のガラス転移温度（Ｔｇ）より高い温度に到達させる［以下、条件（ｂ）という］工程、
を有する電子写真用トナーの製造方法である。
The present invention relates to a powder containing 100 parts by weight of base colored particles containing a binder resin and a colorant, and 4.0 to 7.0 parts by weight of a large particle size silica having a volume median particle size of 30 to 100 nm. ,
(A) Using a mixing device having a mixing blade, the tip peripheral speed of the mixing blade is in the range of 40 to 80 m / sec, and the amount of power energy dropped per unit weight of the powder is 0.01 to 0.05 kwh / kg. (Hereinafter referred to as condition (a)), (b) the temperature of the powder is made to reach a temperature higher than the glass transition temperature (Tg) of the base colored particles [hereinafter referred to as condition (b)]. Process,
A method for producing an electrophotographic toner having the following.
まず、電子写真用トナーの製造に用いる各成分について説明する。
［母体着色粒子］
本発明で用いる母体着色粒子は、少なくとも結着樹脂及び着色剤を含有する。
（結着樹脂）
結着樹脂としては、特に限定されないが、ポリエステル、スチレン−アクリル樹脂等のビニル系樹脂、エポキシ樹脂、ポリカーボネート、ポリウレタン、２種以上の樹脂成分を有するハイブリッド樹脂等が挙げられる。これらの中では、耐久性及び定着性の観点からポリエステルが好ましい。ポリエステルの結着樹脂中の含有量は、好ましくは５０〜１００重量％、より好ましくは７０〜１００重量％、さらに好ましくは１００重量％である。
First, each component used for manufacturing an electrophotographic toner will be described.
[Maternally colored particles]
The matrix colored particles used in the present invention contain at least a binder resin and a colorant.
(Binder resin)
The binder resin is not particularly limited, and examples thereof include vinyl resins such as polyester and styrene-acrylic resins, epoxy resins, polycarbonates, polyurethanes, and hybrid resins having two or more resin components. Among these, polyester is preferable from the viewpoint of durability and fixability. The content of the polyester in the binder resin is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, and still more preferably 100% by weight.
ポリエステルは、公知のカルボン酸成分と公知のアルコール成分とを重縮合させる方法、例えば、特開２００８−０２０８４８号公報に記載の方法により製造することができる。
カルボン酸成分としては、フタル酸、イソフタル酸、テレフタル酸、フマル酸、マレイン酸、アジピン酸、コハク酸等のジカルボン酸、これらの無水物及びこれらの酸のアルキル（炭素数１〜３）エステル；トリメリット酸、ピロメリット酸等の３価以上の多価カルボン酸、それらの酸の無水物及びこれらの酸のアルキル（炭素数１〜３）エステル等が挙げられる。コハク酸としては、無置換のコハク酸以外に、ドデセニルコハク酸、オクテニルコハク酸等の炭素数１〜２０のアルキル基又は炭素数２〜２０のアルケニル基で置換されたコハク酸が挙げられる。
アルコール成分としては、ポリオキシプロピレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシエチレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン等のビスフェノールＡのアルキレン（炭素数２〜３）オキサイド（平均付加モル数１〜１６）付加物；エチレングリコール、プロピレングリコール、グリセリン、ペンタエリスリトール、トリメチロールプロパン、水素添加ビスフェノールＡ、ソルビトール、及びこれらのアルキレン（炭素数２〜４）オキサイド（平均付加モル数１〜１６）付加物等が挙げられる。
The polyester can be produced by a method of polycondensing a known carboxylic acid component and a known alcohol component, for example, a method described in JP-A-2008-020848.
Examples of the carboxylic acid component include dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, adipic acid, and succinic acid, anhydrides thereof, and alkyl (carbon number 1 to 3) esters of these acids; Examples thereof include trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, anhydrides of these acids, and alkyl (carbon number 1 to 3) esters of these acids. Examples of the succinic acid include succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms such as dodecenyl succinic acid and octenyl succinic acid, in addition to unsubstituted succinic acid.
Examples of the alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. Bisphenol A alkylene (2 to 3 carbon atoms) oxide (average added mole number 1 to 16) adduct; ethylene glycol, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, and alkylenes thereof (C2-C4) oxide (average addition mole number 1-16) adduct etc. are mentioned.
ポリエステルは、耐久性及び定着性の観点から、その軟化点が８０〜１６５℃であるのが好ましく、ガラス転移点が５０〜８５℃であるのが好ましく、酸価が０．５〜６０ｍｇＫＯＨ／ｇであるのが好ましい。軟化点、ガラス転移点及び酸価は、縮重合の温度、反応時間等を調節することにより所望のものを得ることができる。なお、該軟化点、ガラス転移点及び酸価は、実施例に記載の方法により測定したものである。 The polyester preferably has a softening point of 80 to 165 ° C, a glass transition point of 50 to 85 ° C, and an acid value of 0.5 to 60 mgKOH / g from the viewpoint of durability and fixability. Is preferred. The desired softening point, glass transition point, and acid value can be obtained by adjusting the condensation polymerization temperature, reaction time, and the like. In addition, this softening point, glass transition point, and acid value are measured by the method as described in an Example.
（着色剤）
着色剤としては、トナー用着色剤として用いられている染料、顔料等を使用することができ、カーボンブラック、フタロシアニンブルー、パーマネントブラウンＦＧ、ブリリアントファーストスカーレット、ピグメントグリーンＢ、ローダミン−Ｂベース、ソルベントレッド４９、ソルベントレッド１４６、ソルベントブルー３５、キナクリドン、カーミン６Ｂ、ジスアゾエロー等が挙げられる。これらは単独で又は２種以上を混合して用いることができる。着色剤の含有量は、結着樹脂１００重量部に対して、好ましくは１〜４０重量部、より好ましくは３〜１０重量部である。
(Coloring agent)
As the colorant, dyes and pigments used as toner colorants can be used. Carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, disazo yellow and the like. These can be used alone or in admixture of two or more. The content of the colorant is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
（添加剤）
母体着色粒子は、結着樹脂及び着色剤に加えて、さらに荷電制御剤、離型剤、流動性向上剤、導電性調整剤、体質顔料、繊維状物質等の補強充填剤、酸化防止剤、老化防止剤、クリーニング性向上剤等の添加剤を適宜含有していてもよい。
荷電制御剤としては、負帯電性及び正帯電性のいずれのものも使用することができる。負帯電性荷電制御剤としては、例えば、含金属アゾ染料、銅フタロシアニン染料、サリチル酸のアルキル誘導体の金属錯体、ニトロイミダゾール誘導体等が挙げられる。正帯電性荷電制御剤としては、例えば、ニグロシン染料、トリフェニルメタン系染料、第四級アンモニウム塩化合物、ポリアミン樹脂、イミダゾール誘導体等が挙げられる。また、樹脂等の高分子タイプのものを使用することもできる。荷電制御剤の含有量は、結着樹脂１００重量部に対して、好ましくは０．１〜８重量部、より好ましくは０．２〜５重量部である。
離型剤としては、ポリプロピレンワックス、ポリエチレンワックス、フィッシャートロプッシュ等の合成ワックス、モンタンワックス等の石炭系ワックス、パラフィンワックス等の石油ワックス、アルコール系ワックス等のワックスが挙げられ、これらのワックスは単独で又は２種以上を混合して用いられていてもよい。離型剤の含有量は、結着樹脂１００重量部に対して、好ましくは１〜２０重量部、より好ましくは２〜１０重量部である。
(Additive)
In addition to the binder resin and the colorant, the base colored particles further include a charge control agent, a release agent, a fluidity improver, a conductivity modifier, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, An additive such as an antiaging agent and a cleaning property improving agent may be appropriately contained.
As the charge control agent, any one of negative chargeability and positive chargeability can be used. Examples of the negatively chargeable charge control agent include metal-containing azo dyes, copper phthalocyanine dyes, metal complexes of salicylic acid alkyl derivatives, and nitroimidazole derivatives. Examples of the positively chargeable charge control agent include nigrosine dyes, triphenylmethane dyes, quaternary ammonium salt compounds, polyamine resins, and imidazole derivatives. Also, a polymer type such as a resin can be used. The content of the charge control agent is preferably 0.1 to 8 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the binder resin.
Examples of mold release agents include polypropylene wax, polyethylene wax, synthetic wax such as Fischer Tropu, coal wax such as montan wax, petroleum wax such as paraffin wax, wax such as alcohol wax, and these waxes are used alone. Or a mixture of two or more thereof. The content of the release agent is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
母体着色粒子は、粉砕トナーであることが好ましい。粉体トナーの製造は、例えば、結着樹脂、着色剤等をヘンシェルミキサー、ボールミル等の混合機で混合した後、密閉式ニーダー又は１軸もしくは２軸の押出機等で溶融混練し、冷却後、ハンマーミル等を用いて粗粉砕し、さらにジェット気流を用いた微粉砕機や機械式粉砕機により微粉砕し、旋回気流を用いた分級機やコアンダ効果を用いた分級機により所定の粒度に分級することにより行なうことができる。
母体着色粒子の体積中位粒径は、トナーの保存安定性及び転写効率の観点から、好ましくは５．５〜９μｍ、より好ましくは６〜９μｍ、さらに好ましくは６．２〜８．８μｍである。該体積中位粒径は、実施例に記載の方法に従って測定したものである。
The matrix coloring particles are preferably pulverized toner. For example, powder toner is manufactured by mixing a binder resin, a colorant, and the like with a mixer such as a Henschel mixer and a ball mill, and then melt-kneading with a hermetic kneader or a single-screw or twin-screw extruder, and cooling. , Coarsely pulverized using a hammer mill, etc., finely pulverized by a fine pulverizer or mechanical pulverizer using a jet stream, and adjusted to a predetermined particle size by a classifier using a swirling airflow or a classifier using the Coanda effect This can be done by classification.
The volume-median particle size of the matrix coloring particles is preferably 5.5 to 9 μm, more preferably 6 to 9 μm, and still more preferably 6.2 to 8.8 μm, from the viewpoint of storage stability and transfer efficiency of the toner. . The volume median particle diameter is measured according to the method described in the examples.
［大粒径シリカ］
大粒径シリカは、その体積中位粒径が３０〜１００ｎｍであり、大粒径シリカの凝集や脱離の抑制及びトナーの転写効率の観点から、好ましくは３５〜８０ｎｍ、より好ましくは３５〜５０ｎｍである。また、大粒径シリカのＢＥＴ比表面積は、大粒径シリカの凝集や脱離の抑制及びトナーの転写効率の観点から、好ましくは２０〜１００ｍ2／ｇ、より好ましくは２５〜７０ｍ2／ｇ、さらに好ましくは３０〜５０ｍ2／ｇである。該体積中位粒径及びＢＥＴ比表面積は、実施例に記載の方法に従って測定したものである。
大粒径シリカの添加量は、母体着色粒子１００重量部に対して４．０〜７．０重量部であり、トナーの流動性及び転写効率の観点から、母体着色粒子１００重量部に対して、好ましくは４．５〜７．０重量部、より好ましくは４．８〜６．８重量部である。
[Large particle size silica]
The large particle size silica has a volume-median particle size of 30 to 100 nm, and preferably 35 to 80 nm, more preferably 35 to 35 nm, from the viewpoint of suppressing aggregation and detachment of the large particle size silica and toner transfer efficiency. 50 nm. Further, BET specific surface area of the large silica, from the viewpoint of transfer efficiency of aggregation or detachment of suppression and the toner having a large particle size silica, preferably 20 to 100 m 2 / g, more preferably 25~70m 2 / g More preferably, it is 30-50 m < 2 > / g. The volume median particle size and BET specific surface area are measured according to the methods described in the examples.
The addition amount of the large particle size silica is 4.0 to 7.0 parts by weight with respect to 100 parts by weight of the base colored particles. From the viewpoint of the fluidity and transfer efficiency of the toner, 100 parts by weight of the base colored particles. , Preferably 4.5 to 7.0 parts by weight, more preferably 4.8 to 6.8 parts by weight.
［母体着色粒子と大粒径シリカの混合方法］
本発明の電子写真用トナーの製造方法は、下記条件（ａ）及び（ｂ）を満たす条件下に母体着色粒子と大粒径シリカとを含有する粉体を混合する工程を有する。
（条件（ａ））
条件（ａ）は、混合羽根を有する混合装置を用いて、混合羽根の先端周速を４０〜８０ｍ／ｓｅｃの範囲、粉体の単位重量当たりに投下する動力エネルギー量を０．０１〜０．０５ｋｗｈ／ｋｇの範囲として粉体を混合するというものである。
混合装置に設けられた混合羽根の先端周速は、４０〜８０ｍ／ｓｅｃの範囲であり、大粒径シリカの分散性の観点から、好ましくは４０〜６５ｍ／ｓｅｃである。混合羽根の先端周速を４０ｍ／ｓｅｃ以上にすることにより、大粒径シリカを良好に分散混合することができ、大粒径シリカの凝集、転写不良による画像濃度の低下及び抜けの発生を抑制することができる。一方、混合羽根の先端周速を８０ｍ／ｓｅｃ以下にすることにより、粉体が融着・固着することや、大粒径シリカおよびその他外添剤が母体着色粒子に深く埋め込まれることを抑制することができる。
[Mixing method of matrix coloring particles and large particle size silica]
The method for producing an electrophotographic toner of the present invention includes a step of mixing a powder containing base color particles and large particle size silica under the conditions satisfying the following conditions (a) and (b).
(Condition (a))
Condition (a) uses a mixing device having mixing blades, the tip peripheral speed of the mixing blades is in the range of 40 to 80 m / sec, and the amount of power energy dropped per unit weight of the powder is 0.01 to 0.00. The powder is mixed in the range of 05 kwh / kg.
The tip peripheral speed of the mixing blade provided in the mixing apparatus is in the range of 40 to 80 m / sec, and preferably 40 to 65 m / sec from the viewpoint of dispersibility of the large particle size silica. By setting the tip peripheral speed of the mixing blade to 40 m / sec or more, large-diameter silica can be dispersed and mixed well, and large-diameter silica aggregation, image density reduction due to poor transfer, and occurrence of omission are suppressed. can do. On the other hand, by controlling the tip peripheral speed of the mixing blade to 80 m / sec or less, the powder can be prevented from being fused and fixed, and the large particle size silica and other external additives from being deeply embedded in the matrix coloring particles. be able to.
本発明においては、混合装置が粉体の単位重量当たりに投下する動力エネルギー量を０．０１〜０．０５ｋｗｈ／ｋｇの範囲となるようにして粉体を混合する。該動力エネルギー量は、大粒径シリカの分散性及び凝集や脱離の抑制の観点、並びにトナーの流動性及び転写効率の観点から、好ましくは０．０１５〜０．０５ｋｗｈ／ｋｇである。
なお、本明細書中、粉体の単位重量当たりに投下する動力エネルギー量とは、粉体１ｋｇ当たりの原動機実負荷積算電力量（ｋｗｈ）をいい、以下の式（Ｉ）で表される。
原動機実負荷平均動力（ｋｗ）×処理時間（ｈ）／粉体量（ｋｇ） （Ｉ）
ここで、原動機実負荷平均動力とは、粉体を含む状態における特定回転数の攪拌により混合装置に掛かる負荷平均動力から、粉体を含まない状態における当該回転数と同一回転数の攪拌により混合装置に掛かる無負荷平均動力を差し引いた値を意味する。
In the present invention, the powder is mixed such that the amount of motive energy dropped by the mixing device per unit weight of the powder is in the range of 0.01 to 0.05 kwh / kg. The amount of kinetic energy is preferably 0.015 to 0.05 kwh / kg from the viewpoints of dispersibility of large particle size silica and suppression of aggregation and desorption, as well as toner fluidity and transfer efficiency.
In the present specification, the amount of power energy dropped per unit weight of the powder refers to the motor actual load integrated power amount (kwh) per kg of the powder, and is represented by the following formula (I).
Motor actual load average power (kw) x processing time (h) / powder amount (kg) (I)
Here, the prime mover actual load average power means mixing from the load average power applied to the mixing device by stirring at a specific rotational speed in a state including powder by stirring at the same rotational speed as that in the state not including powder. It means the value obtained by subtracting the no-load average power applied to the device.
混合装置は、特に限定されないが、混合機能と分散機能を有する攪拌式混合装置が好ましい。例えば、トナーの製造工程において、静電特性及び粉体物性等の調整のために添加される小粒径シリカ（体積中位粒径３０ｎｍ未満）や有機・無機微粒子等の外添剤の混合手段に通常用いられている装置が挙げられる。攪拌式混合装置の市販例としては、ヘンシェルミキサー（三井鉱山株式会社製）、スーパーミキサー（株式会社カワタ製）、ハイスピードミキサー（深江パウテック株式会社製）等の縦型混合槽が挙げられる。構造が簡単で清掃容易性に優れることから、ヘンシェルミキサー（三井鉱山株式会社製）、スーパーミキサー（株式会社カワタ製）がより好ましい。
攪拌式混合装置内の混合羽根の仕様としては、一般の混合・分散処理に用いられる最も標準的な組合せを利用することができ、大粒径シリカの分散性の観点から、図１に示すような同一外径を有する上羽根と下羽根の組み合わせからなる混合羽根が好ましい。
The mixing apparatus is not particularly limited, but a stirring type mixing apparatus having a mixing function and a dispersing function is preferable. For example, a means for mixing external additives such as small particle size silica (volume median particle size less than 30 nm) and organic / inorganic fine particles added to adjust electrostatic properties and powder properties in the toner production process The apparatus normally used is mentioned. Commercially available examples of the stirring mixer include vertical mixing tanks such as Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), super mixer (manufactured by Kawata Co., Ltd.), and high speed mixer (manufactured by Fukae Powtech Co., Ltd.). A Henschel mixer (made by Mitsui Mining Co., Ltd.) and a super mixer (made by Kawata Co., Ltd.) are more preferred because of their simple structure and excellent ease of cleaning.
As the specification of the mixing blade in the stirring type mixing apparatus, the most standard combination used for general mixing / dispersing treatment can be used. From the viewpoint of dispersibility of the large particle size silica, as shown in FIG. A mixing blade composed of a combination of an upper blade and a lower blade having the same outer diameter is preferable.
混合羽根の長さ（上羽根と下羽根がある場合には、それぞれの羽根の長さ）は、大粒径シリカの分散性の観点から、好ましくは５００〜６００ｍｍ、より好ましくは５３０〜５７０ｍｍ、さらに好ましくは５４０〜５６０ｍｍである。
混合羽根の回転数（上羽根と下羽根がある場合、それぞれの羽根の回転数）は、大粒径シリカの分散性の観点から、好ましくは１０００〜２５００ｒ／ｍｉｎ、より好ましくは１２００〜２３００ｒ／ｍｉｎである。
また、混合装置での処理時間は、粉体の単位重量当たりに投下する動力エネルギー量を調整する観点から、好ましくは１９０〜１５００秒、より好ましくは２００〜１２００秒、さらに好ましくは２００〜１０００秒である。
From the viewpoint of dispersibility of the large particle size silica, the length of the mixing blade (when there is an upper blade and a lower blade) is preferably 500 to 600 mm, more preferably 530 to 570 mm, More preferably, it is 540-560 mm.
From the viewpoint of dispersibility of the large particle diameter silica, the rotation speed of the mixing blade is preferably 1000 to 2500 r / min, more preferably 1200 to 2300 r / min. min.
The treatment time in the mixing apparatus is preferably 190 to 1500 seconds, more preferably 200 to 1200 seconds, and still more preferably 200 to 1000 seconds, from the viewpoint of adjusting the amount of power energy dropped per unit weight of the powder. It is.
（条件（ｂ））
条件（ｂ）は、前記条件（ａ）により、粉体の温度を母体着色粒子のガラス転移温度（Ｔｇ）より高い温度に到達させるというものである。なお、該母体着色粒子のガラス転移温度は、実施例に記載した方法により測定したものである。
粉体の凝集を抑制し、トナーの転写特性を向上させる観点から、粉体の温度を好ましくは（母体着色粒子のＴｇ＋５℃）以上、より好ましくは（該Ｔｇ＋８℃）以上に調整し、好ましくは（母体着色粒子のＴｇ＋２０℃）以下、より好ましくは（該Ｔｇ＋１２℃）以下、さらに好ましくは（該Ｔｇ＋１０℃）以下に調整する。粉体の温度を上記範囲にすることにより、粉体の凝集を抑制でき、さらに母体着色粒子が離型剤を含有する場合には離型剤中の低融点物の大粒径シリカへの被覆を抑制できるため、トナーの転写特性が向上する。
粉体の温度は、上記条件（ａ）における混合に起因する熱により、母体着色粒子のＴｇより高い温度に到達させることから、粉体全体の温度を均一に上昇させることができ、高性能の電子写真用トナーを得ることができる。
(Condition (b))
The condition (b) is that the temperature of the powder reaches a temperature higher than the glass transition temperature (Tg) of the matrix colored particles according to the condition (a). In addition, the glass transition temperature of this base coloring particle | grain is measured by the method described in the Example.
From the viewpoint of suppressing the aggregation of the powder and improving the transfer characteristics of the toner, the temperature of the powder is preferably adjusted to (Tg + 5 ° C. of the parent colored particles) or higher, more preferably (Tg + 8 ° C.) or higher, preferably (Tg + 20 ° C. of parent colored particles) or less, more preferably (Tg + 12 ° C.) or less, and further preferably (Tg + 10 ° C.) or less. By setting the temperature of the powder within the above range, the aggregation of the powder can be suppressed, and when the base coloring particles contain a release agent, the low melting point material in the release agent is coated on the large particle size silica. Therefore, the toner transfer characteristics are improved.
Since the temperature of the powder reaches a temperature higher than the Tg of the base colored particles by the heat resulting from the mixing in the condition (a), the temperature of the entire powder can be increased uniformly, An electrophotographic toner can be obtained.
一つの実施形態において、粉体の混合開始時の温度を一定に保ち、粉体の混合条件を安定化する観点から、母体着色粒子及び大粒径シリカを含有する粉体を上記条件（ａ）にて混合する前に、予め該粉体の温度を「（母体着色粒子のＴｇ−４０℃）〜該Ｔｇ」の範囲とすることが好ましい。該粉体の温度は、上記と同様の理由から、好ましくは（該Ｔｇ−１８℃）以上、より好ましくは（該Ｔｇ−１６℃）以上とし、好ましくは（該Ｔｇ−１℃）以下、（該Ｔｇ−２℃）以下とする。
このように、粉体の温度は、混合容器外から熱を加えることによって予め上記温度範囲に調整しておくことができる。混合容器外から熱を加える方法としては、例えば、攪拌式混合装置による低速攪拌（例えば、１０ｍ／ｓｅｃ以下）により加熱する方法や、温水等の熱媒を流通させることができるジャケットを備えた攪拌式混合装置を使用する方法が挙げられる。
In one embodiment, from the viewpoint of keeping the temperature at the start of mixing of the powder constant and stabilizing the mixing condition of the powder, the powder containing the matrix coloring particles and the large particle size silica is added to the above condition (a). It is preferable to set the temperature of the powder in the range of “(Tg of parent colored particles−40 ° C.) to Tg” in advance. The temperature of the powder is preferably (the Tg−18 ° C.) or more, more preferably (the Tg−16 ° C.) or more, preferably (the Tg−1 ° C.) or less, for the same reason as above. Tg-2 ° C.) or less.
Thus, the temperature of the powder can be adjusted in advance to the above temperature range by applying heat from outside the mixing container. As a method of applying heat from outside the mixing vessel, for example, a method of heating by low-speed stirring (for example, 10 m / sec or less) using a stirring type mixing device, or a stirring equipped with a jacket capable of circulating a heat medium such as hot water. The method of using a type | formula mixing apparatus is mentioned.
ジャケットを備えた攪拌式混合装置を使用する場合、ジャケット内の熱媒の温度は、粉体の凝集を抑制し、トナーの転写特性を向上させる観点から、好ましくは母体着色粒子のＴｇ以下、より好ましくは（該Ｔｇ−１℃）以下、さらに好ましくは（該Ｔｇ−２℃）以下になるよう調整する。また、上記と同様の理由から、粉体の温度は、好ましくは（母体着色粒子のＴｇ−２０℃）以上、より好ましくは（該Ｔｇ−１８℃）以上、さらに好ましくは（該Ｔｇ−１６℃）以上になるよう調整する。
ジャケット内の熱媒の温度を母体着色粒子のＴｇ以下に調整することにより、粉体の温度が該Ｔｇ未満かつ熱媒の温度未満の場合、粉体を効率的に加熱することができ、また、粉体の温度が該Ｔｇ以上又は熱媒の温度を超える場合、混合により粉体に加わる熱を効率的に除熱することができる。このようにジャケット流通温度の調整により、粉体を母体着色粒子のＴｇ以上の目標温度に到達させるための混合処理時間、粉体の単位重量当たりに投下する動力エネルギー量を調整することができる。
In the case of using a stirring type mixing device equipped with a jacket, the temperature of the heat medium in the jacket is preferably Tg or less of the base colored particles, from the viewpoint of suppressing the aggregation of the powder and improving the transfer characteristics of the toner. It is preferably adjusted to (the Tg-1 ° C) or less, more preferably (the Tg-2 ° C) or less. Further, for the same reason as described above, the temperature of the powder is preferably (Tg-20 ° C. of the mother colored particles) or more, more preferably (Tg-18 ° C.) or more, and further preferably (Tg-16 ° C.). ) Adjust so that it is above.
By adjusting the temperature of the heating medium in the jacket to be equal to or lower than the Tg of the base coloring particles, the powder can be efficiently heated when the temperature of the powder is lower than the Tg and lower than the temperature of the heating medium. When the temperature of the powder exceeds the Tg or exceeds the temperature of the heating medium, the heat applied to the powder by mixing can be efficiently removed. Thus, by adjusting the jacket circulation temperature, it is possible to adjust the mixing processing time for allowing the powder to reach a target temperature equal to or higher than the Tg of the base colored particles, and the amount of power energy dropped per unit weight of the powder.
上記方法により得られた粉体は、小粒径化や高画質化の観点から、体積中位粒径が、好ましくは４〜１５μｍ、より好ましくは４〜１０μｍである。 The powder obtained by the above method has a volume-median particle size of preferably 4 to 15 μm, more preferably 4 to 10 μm, from the viewpoint of reducing the particle size and improving the image quality.
[その他の処理]
さらに、上記方法により得られた粉体は、静電特性（帯電性等）や粉体特性（流動性等）を向上させる観点から、通常の方法によって（例えば、ヘンシェルミキサー、スーパーミキサー等の高速攪拌可能な混合機によって）、大粒径シリカ以外の他の外添剤で処理を施してもよい。また、この大粒径シリカ以外の他の外添剤は、大粒径シリカと共に添加してもよい。大粒径シリカ以外の他の外添剤としては、無機微粒子や樹脂微粒子等が挙げられる。
無機微粒子としては、アルミナ、酸化チタン、ジルコニア、酸化錫、酸化亜鉛、小粒径シリカ等が挙げられ、特開平８−２２０８００号公報に記載のものも使用することができる。なお、小粒径シリカの体積中位粒径は３０ｎｍ未満であり、好ましくは２〜２０ｎｍ、より好ましくは５〜１５ｎｍ、さらに好ましくは５〜１０ｎｍである。また、酸化チタンの体積中位粒径に特に制限は無いが、好ましくは２〜５０ｎｍ、より好ましくは５〜３０ｎｍ、さらに好ましくは１０〜１５ｎｍである。これらの中でも、帯電性の観点から、小粒径シリカ及び酸化チタンが好ましい。他の外添剤として無機微粒子を使用する場合、無機微粒子の合計使用量は、母体着色粒子１００重量部に対して、０．０５〜２重量部が好ましく、０．１〜１．５重量部がより好ましい。
[Other processing]
Furthermore, the powder obtained by the above method can be obtained by a usual method (for example, Henschel mixer, super mixer, etc.) from the viewpoint of improving electrostatic properties (chargeability, etc.) and powder properties (fluidity, etc.). The mixture may be treated with an external additive other than the large particle size silica (by a stirrable mixer). Further, other external additives other than the large particle size silica may be added together with the large particle size silica. Examples of external additives other than the large particle size silica include inorganic fine particles and resin fine particles.
Examples of the inorganic fine particles include alumina, titanium oxide, zirconia, tin oxide, zinc oxide, small particle size silica and the like, and those described in JP-A-8-220800 can also be used. The volume median particle size of the small particle size silica is less than 30 nm, preferably 2 to 20 nm, more preferably 5 to 15 nm, and further preferably 5 to 10 nm. Moreover, there is no restriction | limiting in particular in the volume median particle diameter of a titanium oxide, However, Preferably it is 2-50 nm, More preferably, it is 5-30 nm, More preferably, it is 10-15 nm. Among these, small particle size silica and titanium oxide are preferable from the viewpoint of chargeability. When inorganic fine particles are used as another external additive, the total amount of the inorganic fine particles used is preferably 0.05 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the base colored particles. Is more preferable.
樹脂微粒子としては、メラミン系樹脂微粒子が好ましい。メラミン系樹脂微粒子は、特開２００５−１９５６９４号公報に記載のものを使用することができる。樹脂微粒子の体積中位粒径に特に制限は無いが、好ましくは１０〜５００ｎｍ、より好ましくは５０〜３００ｎｍ、さらに好ましくは１５０〜２５０ｎｍである。他の外添剤として樹脂微粒子を使用する場合、樹脂微粒子の使用量は、定着ローラー表面のチャージアップ防止の観点から、母体着色粒子１００重量部に対して０．０１〜１重量部が好ましく、０．０５〜０．６重量部がより好ましく、０．１５〜０．６重量部がさらに好ましい。 As the resin fine particles, melamine resin fine particles are preferable. As the melamine resin fine particles, those described in JP-A-2005-195694 can be used. Although there is no restriction | limiting in particular in the volume median particle diameter of resin fine particle, Preferably it is 10-500 nm, More preferably, it is 50-300 nm, More preferably, it is 150-250 nm. When resin fine particles are used as another external additive, the amount of resin fine particles used is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the base colored particles from the viewpoint of preventing charge-up on the surface of the fixing roller. 0.05-0.6 weight part is more preferable, and 0.15-0.6 weight part is further more preferable.
なお、大粒径シリカ以外の他の外添剤の合計使用量は、母体着色粒子１００重量部に対して、０．０１〜１０重量部が好ましく、０．１〜５重量部がより好ましく、０．５〜２重量部がさらに好ましい。
上記のように他の外添剤で処理した粉体の体積中位粒径は、好ましくは５．５〜１０μｍ、より好ましくは６〜９μｍ、さらに好ましくは６．４〜８．６μｍである。該体積中位粒径は、実施例に記載の方法に従って測定したものである。
The total amount of external additives other than silica having a large particle diameter is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the base colored particles. 0.5-2 weight part is further more preferable.
The volume median particle size of the powder treated with other external additives as described above is preferably 5.5 to 10 μm, more preferably 6 to 9 μm, and further preferably 6.4 to 8.6 μm. The volume median particle diameter is measured according to the method described in the examples.
本発明の方法によって得られる電子写真用トナーは、黒トナー、カラートナー、フルカラートナーのいずれであってもよい。各色の電子写真用トナーは、そのまま一成分現像用トナーとして、又はキャリアと混合して二成分現像剤として、組み合わせてカラートナーセットとして用いることができ、該トナーセットを用いて、良好なフルカラー画像を形成することができる。 The electrophotographic toner obtained by the method of the present invention may be any of black toner, color toner, and full color toner. Each color electrophotographic toner can be used as a one-component developing toner as it is, or as a two-component developer by mixing with a carrier, and used as a color toner set in combination. Can be formed.
実施例及び比較例で利用した各種分析方法の条件を以下に示す。
［軟化点］
フローテスター「ＣＦＴ−５００Ｄ」（株式会社島津製作所製）を用い、１ｇの試料を昇温速度６℃／分で加熱しながら、プランジャーにより１．９６ＭＰａの荷重を与え、直径１ｍｍ、長さ１ｍｍのノズルから押し出した。温度に対し、フローテスターのプランジャー降下量をプロットし、試料の半量が流出する温度を軟化点とした。
［ガラス転移温度］
示差走査熱量計「ＤＳＣ２１０」（セイコー電子工業株式会社製）を用いて２００℃まで昇温し、その温度から降温速度５０℃／分で−１０℃まで冷却した樹脂サンプルを昇温速度１０℃／分で昇温し、吸熱の最高ピーク温度以下のベースラインの延長線とピークの立ち上がり部分からピークの頂点までの最大傾斜を示す接線との交点の温度とした。
なお、母体着色粒子のガラス転移温度は、該粒子をそのまま用いて、上記同様の方法で測定した。
［酸価］
ＪＩＳ Ｋ００７０の方法に基づき測定した。但し、測定溶媒のみＪＩＳ Ｋ００７０の規定のエタノールとエーテルの混合溶媒から、アセトンとトルエンの混合溶媒（アセトン：トルエン＝１：１（容量比））に変更した。
The conditions of various analysis methods used in Examples and Comparative Examples are shown below.
[Softening point]
Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger, a diameter of 1 mm, and a length of 1 mm. Extruded from the nozzle. The plunger drop amount of the flow tester was plotted against the temperature, and the temperature at which half the sample flowed out was defined as the softening point.
[Glass-transition temperature]
Using a differential scanning calorimeter “DSC210” (manufactured by Seiko Denshi Kogyo Co., Ltd.), the temperature of the resin sample was raised to 200 ° C. and cooled to −10 ° C. at a temperature lowering rate of 50 ° C./min. The temperature was raised in minutes, and was defined as the temperature at the intersection of the baseline extension line below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.
The glass transition temperature of the base colored particles was measured by the same method as above using the particles as they were.
[Acid value]
It measured based on the method of JISK0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).
［外添剤（大粒径シリカ及びその他の外添剤）の体積中位粒径］
外添剤（大粒径シリカ及びその他の外添剤）の体積中位粒径は、以下の装置及び条件で測定した。
測定装置：レーザー回折型粒径測定機（株式会社堀場製作所製、ＬＡ−９２０）
測定条件：測定用セルに蒸留水を加え、吸光度を適正範囲になる温度で体積中位粒径（Ｄ50）を測定した。
[Volume-median particle size of external additives (large particle size silica and other external additives)]
The volume median particle size of the external additives (large particle size silica and other external additives) was measured with the following apparatus and conditions.
Measuring device: Laser diffraction type particle size measuring machine (LA-920, manufactured by HORIBA, Ltd.)
Measurement conditions: Distilled water was added to the measurement cell, and the volume-median particle size (D 50 ) was measured at a temperature at which the absorbance was in an appropriate range.
［母体着色粒子及び電子写真用トナーの体積中位粒径］
母体着色粒子及び電子写真用トナーの体積中位粒径は、以下の装置及び条件で測定した。
測定機：コールターマルチサイザーII（ベックマンコールター社製）
アパチャー径：１００μｍ
解析ソフト：コールターマルチサイザーアキュコンプ バージョン１．１９（ベックマンコールター社製）
電解液：アイソトンII（ベックマンコールター社製）
分散液：「エマルゲン（登録商標）１０９Ｐ」（花王株式会社製、ポリオキシエチレンラウリルエーテル、ＨＬＢ：１３．６）を前記電解液に溶解させ、濃度５重量％の分散液を得た。
分散条件：前記分散液５ｍＬに測定試料１０ｍｇを添加し、超音波分散機にて１分間分散させ、その後、電解液２５ｍＬを添加し、さらに、超音波分散機にて１分間分散させて、試料分散液を作製した。
測定条件：前記試料分散液を前記電解液１００ｍＬに加えることにより、３万個の粒子の粒径を２０秒で測定できる濃度に調整した後、３万個の粒子を測定し、その粒度分布から体積中位粒径（Ｄ50）を求めた。
[Volume Median Particle Size of Base Colored Particles and Electrophotographic Toner]
The volume median particle size of the matrix coloring particles and the electrophotographic toner was measured by the following apparatus and conditions.
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 100 μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter, Inc.)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: “Emulgen (registered trademark) 109P” (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by weight.
Dispersion condition: 10 mg of a measurement sample is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 mL of electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. A dispersion was prepared.
Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size distribution is determined. The volume median particle size (D 50 ) was determined.
［大粒径シリカのＢＥＴ比表面積］
Ｍｉｃｒｏｍｅｒｉｔｉｃｓ ＦｌｏｗＳｏｒｂIII（株式会社島津製作所製）を用いて、下記条件でＢＥＴ比表面積を測定した。
トナーサンプル量：約０．１ｇ
脱気条件：４０℃、１０分間
吸着ガス：窒素ガス
[BET specific surface area of large particle size silica]
A BET specific surface area was measured under the following conditions using Micromeritics FlowSorbIII (manufactured by Shimadzu Corporation).
Toner sample amount: about 0.1 g
Degassing conditions: 40 ° C., 10 minutes Adsorbed gas: Nitrogen gas
［母体着色粒子への大粒径シリカの被覆率］
母体着色粒子への大粒径シリカの被覆率は、以下の式により算出した。なお、本実施例に用いた母体着色粒子の比重は１．３ｇ／ｍｌであり、大粒径シリカの体積中位粒子径は４０ｎｍであり、大粒径シリカの比重は２．２ｇ／ｍｌであった。
被覆率＝（３1/2×Ｄｔ×бｔ）／（２π×ｄ×б）
Ｄｔ：母体着色粒子の体積中位粒子径
бｔ：母体着色粒子の比重
ｄ ：大粒径シリカの体積中位粒子径
б ：大粒径シリカの比重
[Coating ratio of large particle size silica to matrix colored particles]
The coverage of the large particle size silica on the matrix colored particles was calculated by the following formula. The specific gravity of the matrix colored particles used in this example is 1.3 g / ml, the volume median particle size of the large particle size silica is 40 nm, and the specific gravity of the large particle size silica is 2.2 g / ml. there were.
Coverage ratio = (3 1/2 × Dt × бt) / (2π × d × б)
Dt: Volume median particle diameter of matrix colored particles бt: Specific gravity of matrix colored particles d: Volume median particle diameter of large silica particles б: Specific gravity of large silica particles
実施例及び比較例で得られた印字画像濃度、転写後のベルト残量、現像ローラー上のトナーの帯電量及び現像ローラー上のトナーの付着量は、「ＬＢＰ−５２００」（Ａ４ Ｃｏｌｏｒ ４ｐｐｍ、Ｂｌａｃｋ１９ｐｐｍ、キヤノン株式会社製）を改造し、以下の通りに行った。
［印字画像濃度］
初期（画像印字３０枚以内）評価にて、１６ｍｍ四角形のべた画像を、Ａ４に５箇所（右上、左上、真ん中、右下、左下）作製し、それぞれをグレタグ濃度計「Ｓｐｅｃｔｒｏ Ｅｙｅ」（グレタグ・マクベス社製）で測定し、その平均値を算出し、以下の基準に従って評価した。
（評価基準）
１：１．００以上
２：０．９０以上〜１．００未満
３：０．８０以上〜０．９０未満
４：０．６８以上〜０．８０未満
５：０．６８未満
The print image density obtained in the examples and comparative examples, the remaining amount of the belt after transfer, the charge amount of the toner on the development roller, and the adhesion amount of the toner on the development roller are “LBP-5200” (A4 Color 4 ppm, Black 19 ppm). , Manufactured by Canon Inc.) and modified as follows.
[Print image density]
In the initial evaluation (within 30 images printed), 16 mm square solid images were created in A4 at 5 locations (upper right, upper left, middle, lower right, lower left), and each of them was a Gretag densitometer “Spectro Eye” The average value was calculated and evaluated according to the following criteria.
(Evaluation criteria)
1: 1.00 or more 2: 0.90 or more to less than 1.00 3: 0.80 or more to less than 0.90 4: 0.68 or more to less than 0.80 5: less than 0.68
［転写後のベルト残量］
初期（画像印字３０枚以内）評価にて、ベタ画像を通紙途中で止め、転写後の部分を、転写ベルトからメンディングテープ「Ｓｃｏｔｃｈ（登録商標） ８１０」（幅１８ｍｍ、住友スリーエム株式会社製）にとり、メンディングテープ単体との差をグレタグ濃度計「Ｓｐｅｃｔｒｏ Ｅｙｅ」（グレタグ・マクベス社製）で測定し、以下の基準に従って評価した。
（評価基準）
Ａ：０．０７以下
Ｂ：０．０８以上
[Remaining belt after transfer]
In the initial evaluation (within 30 image prints), the solid image was stopped halfway through the paper, and the transferred part was transferred from the transfer belt to a mending tape “Scotch (registered trademark) 810” (width 18 mm, manufactured by Sumitomo 3M Limited). ) Was measured with a Gretag densitometer “Spectro Eye” (manufactured by Gretag Macbeth) and evaluated according to the following criteria.
(Evaluation criteria)
A: 0.07 or less B: 0.08 or more
［現像ローラー上のトナーの帯電量］
初期（画像印字３０枚以内）評価にて、白紙を３枚通紙し、その後、現像ローラー上のトナーを、吸引式帯電量測定装置「２１０ＨＳ−２Ａ」（Ｑ／Ｍメーター、トレック・ジャパン株式会社製）にて吸引して測定した。
［現像ローラー上のトナーの付着量］
初期（画像印字３０枚以内）評価にて、白紙を３枚通紙し、その後、現像ローラー上のトナーを、吸引式帯電量測定装置「２１０ＨＳ−２Ａ」（Ｑ／Ｍメーター、トレック・ジャパン株式会社製）にて吸引して測定した。
[Charge amount of toner on developing roller]
In the initial evaluation (within 30 images printed), 3 sheets of white paper were passed, and then the toner on the developing roller was charged with a suction-type charge measurement device “210HS-2A” (Q / M meter, Trek Japan Co., Ltd.) Measured with suction.
[Amount of toner adhering to developing roller]
In the initial evaluation (within 30 images printed), 3 sheets of white paper were passed, and then the toner on the developing roller was charged with a suction-type charge measurement device “210HS-2A” (Q / M meter, Trek Japan Co., Ltd.) Measured with suction.
製造例１（ポリエステルＡの製造）
ポリオキシプロピレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン３３０８ｇ、ポリオキシエチレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン３４１ｇ、フマル酸７９２ｇ及びターシャリーブチルカテコール５ｇを、窒素導入管、脱水管、攪拌機及び熱電対を装備した内容積５Ｌの四つ口フラスコに入れ、窒素雰囲気下、１８０℃から２１０℃まで５時間かけて昇温して反応させた後、さらに８ｋＰａにて１時間反応を行った。
次いで、無水トリメリット酸４８０ｇを投入し、常圧にて１時間反応させた後、さらに８ｋＰａにて軟化点が１４５．３℃に達するまで反応を行い、結着樹脂（以下、ポリエステルＡと称する）を得た。得られたポリエステルＡのガラス転移温度は６３．８℃、酸価は３５．０であった。
Production Example 1 (Production of polyester A)
3308 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 341 g of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 792 g of fumaric acid and 5 g of tertiary butyl catechol was placed in a 5 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, and heated from 180 ° C. to 210 ° C. over 5 hours under a nitrogen atmosphere. After the reaction, the reaction was further carried out at 8 kPa for 1 hour.
Next, after adding 480 g of trimellitic anhydride and reacting at normal pressure for 1 hour, the reaction was further continued at 8 kPa until the softening point reached 145.3 ° C., and a binder resin (hereinafter referred to as polyester A) was obtained. ) Polyester A obtained had a glass transition temperature of 63.8 ° C. and an acid value of 35.0.
製造例２（ポリエステルＢの製造）
ポリオキシプロピレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン８８２ｇ、ポリオキシエチレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン２５９４ｇ、テレフタル酸１４９９ｇ及び２−エチルヘキサン酸錫２５ｇを、窒素導入間、脱水管、攪拌器及び熱電対を装備した内容積５Ｌの四つ口フラスコに入れ、窒素雰囲気下、２３０℃で８時間反応させた後、さらに８ｋＰａにて軟化点が１００．４℃に達するまで反応を行い、結着樹脂（ポリエステルＢ）を得た。得られたポリエステルＢのガラス転移温度は６０．２℃、酸価は２．４であった。
Production Example 2 (Production of polyester B)
882 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 2594 g of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1499 g of terephthalic acid and 25 g of tin 2-ethylhexanoate was placed in a 5 L four-necked flask equipped with a dehydrating tube, a stirrer and a thermocouple during nitrogen introduction, and reacted at 230 ° C. for 8 hours in a nitrogen atmosphere. The reaction was performed at 8 kPa until the softening point reached 100.4 ° C. to obtain a binder resin (polyester B). Polyester B obtained had a glass transition temperature of 60.2 ° C. and an acid value of 2.4.
製造例３（母体着色粒子Ｘの製造）
ポリエステルＡ ４６．０重量部、ポリエステルＢ ４６．０重量部、荷電制御剤「ＬＲ−１４７」（日本カーリット株式会社製）０．５重量部、離型剤「カルナバワックス」（植物系ワックス、株式会社加藤洋行製）３．０重量部、離型剤「ＨＮＰ−９」（パラフィン系ワックス、日本精鑞株式会社製）１．５重量部及び着色剤「ＥＣＲ−１０１」（ＰＲ−５７：１、大日精化工業株式会社製）３．０重量部を予めヘンシェルミキサ（三井鉱山株式会社製）を用いて混合した後、二軸押出機ＰＣＭ（株式会社池貝製）により１００℃で溶融混練し、次いで衝突版式粉砕機ディスパージョンセパレータ（日本ニューマチック工業株式会社製）を用いて粉砕及び分級を行い、体積中位粒径８．５μｍ（粒径５μｍ以下の粒子の体積：２．８％）でＴｇが６０．４℃の母体着色粒子Ｘを得た。
Production Example 3 (Production of parent colored particles X)
46.0 parts by weight of polyester A, 46.0 parts by weight of polyester B, 0.5 part by weight of charge control agent “LR-147” (manufactured by Nippon Carlit Co., Ltd.), release agent “carnauba wax” (plant-based wax, stock Yoko Kato Co., Ltd.) 3.0 parts by weight, release agent “HNP-9” (paraffin wax, manufactured by Nippon Seiki Co., Ltd.) and colorant “ECR-101” (PR-57: 1 In addition, 3.0 parts by weight of Dainichi Seika Kogyo Co., Ltd.) were mixed in advance using a Henschel mixer (Mitsui Mining Co., Ltd.) and then melt-kneaded at 100 ° C. using a twin screw extruder PCM (Ikegai Co., Ltd.). Then, pulverization and classification were performed using a collision type pulverizer dispersion separator (manufactured by Nippon Pneumatic Industry Co., Ltd.), and the volume median particle size was 8.5 μm (the volume of particles having a particle size of 5 μm or less: 2.8%). At T There was obtained mother colored particles X of 60.4 ° C..
製造例４（母体着色粒子Ｙの製造）
ポリエステルＡ ４６．０重量部、ポリエステルＢ ４６．０重量部、荷電制御剤「ＬＲ−１４７」（日本カーリット株式会社製）０．５重量部、離型剤「カルナバワックス」（植物系ワックス、株式会社加藤洋行製）３．０重量部、離型剤「ＨＮＰ−９」（パラフィン系ワックス、日本精鑞株式会社製）１．５重量部及び着色剤「ＥＣＲ−１０１」（ＰＲ−５７：１、大日精化工業株式会社製）３．０重量部を予めヘンシェルミキサ（三井鉱山株式会社製）を用いて混合した後、二軸押出機ＰＣＭ（株式会社池貝製）により１００℃で溶融混練し、次いで衝突版式粉砕機ディスパージョンセパレータ（日本ニューマチック工業株式会社製）を用いて粉砕及び分級を行い、体積中位粒径６．５μｍ（粒径４μｍ以下の粒子の体積：１．３％）でＴｇが６０．４℃の母体着色粒子Ｙを得た。
Production Example 4 (Production of matrix colored particles Y)
46.0 parts by weight of polyester A, 46.0 parts by weight of polyester B, 0.5 part by weight of charge control agent “LR-147” (manufactured by Nippon Carlit Co., Ltd.), release agent “carnauba wax” (plant-based wax, stock Yoko Kato Co., Ltd.) 3.0 parts by weight, release agent “HNP-9” (paraffin wax, manufactured by Nippon Seiki Co., Ltd.) and colorant “ECR-101” (PR-57: 1 In addition, 3.0 parts by weight of Dainichi Seika Kogyo Co., Ltd.) were mixed in advance using a Henschel mixer (Mitsui Mining Co., Ltd.) and then melt-kneaded at 100 ° C. using a twin screw extruder PCM (Ikegai Co., Ltd.). Then, pulverization and classification are performed using a collision type pulverizer dispersion separator (manufactured by Nippon Pneumatic Industry Co., Ltd.), and the volume-median particle size is 6.5 μm (volume of particles having a particle size of 4 μm or less: 1.3%). At T There was obtained mother colored particles Y of 60.4 ° C..
実施例１
製造例３により得られた母体着色粒子Ｘ １００重量部に、体積中位粒子径４０ｎｍ及びＢＥＴ比表面積４４ｍ2／ｇの大粒径シリカ５．０重量部を添加して、大粒径シリカによって被覆された粒子粉体を得た（粒子のシリカ被覆率は１０３．１％であった）。
得られた粒子粉体を、図１に示したＳＴ型の上羽根とＡ０型の下羽根を組み合わせた混合羽根（羽根の長さ：それぞれ５５０ｍｍ）を備え、かつ温水を流通させたジャケット（ジャケット内の水温：４５℃）を備えた内容積１５０Ｌのヘンシェルミキサー「ＦＭ−１５０型」（三井鉱山株式会社製）によって、混合羽根（上羽根及び下羽根）の回転数１４４０ｒ／ｍｉｎ及び先端周速４１．５ｍ／ｓの処理条件にて１５分間混合することにより、体積中位粒径８．５μｍの粉体が得られた。なお、ヘンシェルミキサーによって粉体の単位重量当たりに投下された動力エネルギー量は０．０３９ｋｗｈ／ｋｇであり、粉体の温度は、最大６５．６℃まで上昇した。
次いで、この得られた粉体に、さらに他の外添剤として小粒径シリカ（体積中位粒径：８ｎｍ）０．８重量部、酸化チタン（体積中位粒径：１２ｎｍ）０．２重量部及びメラミン系樹脂微粒子（体積中位粒径：２００ｎｍ）０．２重量部を添加し、混合羽根（上羽根及び下羽根）の回転数１４４０ｒ／ｍｉｎ及び先端周速４１ｍ／ｓｅｃで３分間混合することにより、トナーを製造した。
Example 1
To 100 parts by weight of the base colored particles X obtained in Production Example 3, 5.0 parts by weight of a large particle size silica having a volume-median particle diameter of 40 nm and a BET specific surface area of 44 m 2 / g are added. A coated particle powder was obtained (silica coverage of the particles was 103.1%).
The obtained particle powder was provided with a mixing blade (blade length: 550 mm each) in which the ST type upper blade and the A0 type lower blade shown in FIG. 1 were combined, and warm water was circulated (jacket) Henshell mixer “FM-150 type” (made by Mitsui Mining Co., Ltd.) with an internal volume of 150 L equipped with an inner water temperature of 45 ° C. and a rotating speed of the mixing blade (upper blade and lower blade) of 1440 r / min and tip peripheral speed By mixing for 15 minutes under a treatment condition of 41.5 m / s, a powder having a volume-median particle size of 8.5 μm was obtained. The amount of kinetic energy dropped per unit weight of the powder by the Henschel mixer was 0.039 kwh / kg, and the temperature of the powder rose to a maximum of 65.6 ° C.
Next, 0.8 parts by weight of small particle size silica (volume median particle size: 8 nm) and titanium oxide (volume median particle size: 12 nm) 0.2 are added to the obtained powder as further external additives. Part by weight and 0.2 part by weight of melamine resin fine particles (volume median particle size: 200 nm) are added, and the mixing blade (upper blade and lower blade) has a rotational speed of 1440 r / min and a tip peripheral speed of 41 m / sec for 3 minutes. The toner was manufactured by mixing.
実施例２〜５
実施例１において、表１に示す条件に変更したこと以外は、実施例１と同様の操作により、トナーを製造した。
Examples 2-5
A toner was produced in the same manner as in Example 1 except that the conditions in Example 1 were changed to those shown in Table 1.
実施例６〜９
実施例１において、製造例３により得られた母体着色粒子Ｘの代わりに製造例４により得られた母体着色粒子Ｙを用い、且つ表１に示す条件に変更したこと以外は、実施例１と同様の操作により、トナーを製造した。
Examples 6-9
In Example 1, except that the matrix colored particles Y obtained in Production Example 4 were used instead of the matrix colored particles X obtained in Production Example 3, and the conditions shown in Table 1 were changed, Example 1 and A toner was manufactured in the same manner.
比較例１〜９
実施例１において、表２に示す条件に変更したこと以外は、実施例１と同様の操作により、トナーを製造した。
Comparative Examples 1-9
A toner was manufactured in the same manner as in Example 1 except that the conditions in Example 1 were changed to those shown in Table 2.
比較例１０
実施例１において、製造例３により得られた母体着色粒子Ｘの代わりに製造例４により得られた母体着色粒子Ｙを用い、且つ表２に示す条件に変更したこと以外は、実施例１と同様の操作により、トナーを製造した。
Comparative Example 10
Example 1 is different from Example 1 except that the matrix colored particles Y obtained in Production Example 4 are used in place of the matrix colored particles X obtained in Production Example 3 and the conditions shown in Table 2 are changed. A toner was manufactured in the same manner.
表１より、本発明の製造方法に従って製造したトナーは、いずれも印字画像濃度が高く、さらに、転写後のベルトへのトナーの残量が少なく、優れた転写効率を有していることが分かる。
一方、表２の比較例１〜４では、混合羽根（上羽根及び下羽根）の先端周速が４０ｍ／ｓｅｃ未満であり、攪拌熱による粉体の温度上昇が小さいため、粉体の温度を高めるためにジャケット通水温度を高くした。混合羽根の先端周速が小さいため、粉体の単位重量当たりに投下する動力エネルギー量を本発明の０．０１〜０．０５ｋｗｈ／ｋｇの範囲に調整すべく、混合処理時間を長くしている。その結果、何れについても、混合粉体の固着や凝集が発生し、印字画像濃度と転写効率の両方を満足するトナーを得ることはできなかった。大粒径シリカの添加量を本発明の下限値よりも少量にした比較例１及び２では、固着凝集が強く、特に比較例１ではトナーとして評価できなかった。また、比較例３及び４は、大粒径シリカの添加量が本発明の範囲内であり、比較例２に比べて若干、混合粉体の凝集が抑制されているが、攪拌条件が本発明と異なるために印字画像濃度は目標に達していない。
比較例５、７及び１０では、混合羽根（上羽根及び下羽根）の先端周速を本発明の範囲としているが、粉体の単位重量当たりに投下する動力エネルギー量を本発明の範囲の０．０５ｋｗｈ／ｋｇを超えており、その結果、印字画像濃度の低下もしくは転写後のベルトへのトナーの残量が増加しており、良好な結果を得ることができなかった。
比較例６では、混合羽根（上羽根及び下羽根）の先端周速を本発明の範囲としているが、粉体の単位重量当たりに投下する動力エネルギー量を本発明の範囲の０．０１ｋｗｈ／ｋｇ未満となっており、その結果、印字画像濃度の低下し、良好な結果を得ることができなかった。
比較例８では、粉体温度がＴｇ以上に達しており、転写効率の大幅な低下は確認されなかったものの、粉体の単位重量当たりに投下する動力エネルギー量が０．０５ｋｗｈ／ｋｇを超えており、得られた粉体には若干の凝集物が確認された。
比較例９では、粉体の単位重量当たりに投下する動力エネルギー量を本発明の０．０１〜０．０５ｋｗｈ／ｋｇの範囲であり、その結果、印字画像濃度及び転写後のベルトへのトナーの残量では良好な結果を得ることが出来ているが、混合羽根（上羽根及び下羽根）の先端周速が８０ｍ／ｓｅｃを超えており、得られた粉体には若干の凝集物が確認された。
From Table 1, it can be seen that all of the toners manufactured according to the manufacturing method of the present invention have a high print image density, a small amount of toner remaining on the belt after transfer, and excellent transfer efficiency. .
On the other hand, in Comparative Examples 1 to 4 in Table 2, the tip peripheral speed of the mixing blade (upper blade and lower blade) is less than 40 m / sec, and the temperature rise of the powder due to the heat of stirring is small. In order to increase, the jacket water temperature was raised. Since the tip peripheral speed of the mixing blade is small, the mixing processing time is lengthened to adjust the amount of power energy dropped per unit weight of the powder to the range of 0.01 to 0.05 kwh / kg of the present invention. . As a result, in both cases, the mixed powder was fixed and agglomerated, and it was impossible to obtain a toner satisfying both the print image density and the transfer efficiency. In Comparative Examples 1 and 2 in which the addition amount of the large particle size silica was smaller than the lower limit of the present invention, the fixation and aggregation was strong, and in Comparative Example 1, the toner could not be evaluated. In Comparative Examples 3 and 4, the addition amount of the large particle size silica is within the range of the present invention, and the agglomeration of the mixed powder is slightly suppressed as compared with Comparative Example 2, but the stirring condition is the present invention. Therefore, the printed image density does not reach the target.
In Comparative Examples 5, 7 and 10, the tip peripheral speeds of the mixing blades (upper blade and lower blade) are within the scope of the present invention, but the amount of power energy dropped per unit weight of the powder is 0 within the scope of the present invention. As a result, the print image density decreased or the remaining amount of toner on the belt after transfer increased, and good results could not be obtained.
In Comparative Example 6, the tip peripheral speed of the mixing blade (upper blade and lower blade) is within the range of the present invention, but the amount of power energy dropped per unit weight of the powder is 0.01 kwh / kg within the range of the present invention. As a result, the print image density was lowered, and good results could not be obtained.
In Comparative Example 8, although the powder temperature reached Tg or higher and no significant reduction in transfer efficiency was confirmed, the amount of power energy dropped per unit weight of the powder exceeded 0.05 kwh / kg. Some agglomerates were confirmed in the obtained powder.
In Comparative Example 9, the amount of power energy dropped per unit weight of the powder is in the range of 0.01 to 0.05 kwh / kg of the present invention. As a result, the print image density and the toner on the belt after transfer Good results were obtained with the remaining amount, but the tip peripheral speed of the mixing blade (upper blade and lower blade) exceeded 80 m / sec, and some agglomerates were confirmed in the obtained powder. It was done.
本発明により得られるトナーは、大粒径シリカの凝集や脱離が少なく、かつ母体着色粒子表面上への大粒径シリカの均一分散が十分である。そのためトナーの付着力が小さく、転写効率に優れており、高い画像濃度が得られるため、電子写真用トナーとして有用である。 The toner obtained according to the present invention has little aggregation and detachment of the large particle size silica, and uniform dispersion of the large particle size silica on the surface of the base colored particles is sufficient. Therefore, the adhesive force of the toner is small, the transfer efficiency is excellent, and a high image density can be obtained. Therefore, the toner is useful as an electrophotographic toner.
Claims (6)
（ａ）混合羽根を有する混合装置を用いて、混合羽根の先端周速を４０〜８０ｍ／ｓｅｃの範囲、粉体の単位重量当たりに投下する動力エネルギー量を０．０１〜０．０５ｋｗｈ／ｋｇの範囲として混合することにより、（ｂ）粉体の温度を母体着色粒子のガラス転移温度（Ｔｇ）より高い温度に到達させる工程、
を有する電子写真用トナーの製造方法。 A powder containing 100 parts by weight of matrix colored particles containing a binder resin and a colorant, and 4.5 to 7.0 parts by weight of a large particle size silica having a volume median particle size of 30 to 100 nm,
(A) Using a mixing device having a mixing blade, the tip peripheral speed of the mixing blade is in the range of 40 to 80 m / sec, and the amount of power energy dropped per unit weight of the powder is 0.01 to 0.05 kwh / kg. (B) a step of causing the temperature of the powder to reach a temperature higher than the glass transition temperature (Tg) of the base colored particles by mixing as a range of
A method for producing an electrophotographic toner comprising:
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